| 160109-60-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• CAS: 160109-60-4
• 化学式: C₁₄H₂₁ISi
• 分子量: 344.311
• InChiKey: JGDBBHATYNLABR-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  六羰基钨 、 、 三氟甲烷磺酸甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 以55%的产率得到carbon monoxide;[(E)-1-methoxy-12-trimethylsilyldodec-2-en-6,11-diynylidene]tungsten
  参考文献：
  名称：

  Three-Component Intramolecular Two-Alkyne Annulations of Fischer Carbene Complexes: New Strategies for Steroid Synthesis

  摘要：

  The two-alkyne annulations of a variety of chromium and tungsten carbene complexes are examined in which both of the alkynes are tethered to the carbene complex. The reactions of complexes in which the two alkynes and the first alkyne and the carbene carbon are connected by methylene groups were investigated for their potential in the construction of tricyclic phenols. This methodology was screened for a number of different ring sizes, and it was found that the efficiency of phenol formation depended on the nature of the metal, the solvent, and the sizes of the rings produced. In the reactions of chromium complexes, for certain ring sizes an unprecedented lactone product was also observed which resulted from the incorporation of the two alkynes as well as two carbon monoxide ligands from the metal. A new strategy for entry to the tetracyclic ring system of steroids is developed that involves a tandem coupling of a Diels-Alder reaction of carbene complexes with the double-intramolecular two-alkyne annulation. In a model system where the A and C rings are aromatic, the feasibility of this strategy was demonstrated in a reaction where all four rings of the steroid ring system can be generated in a one-pot reaction. In a second generation of this strategy, it was demonstrated that the tandem coupling of these reactions can also lead to the generation of nonaromatic steroidal ring systems.

  DOI：

  10.1021/ja00096a019
• 作为产物：
  描述：

  1,6-庚二炔 在 正丁基锂 、 乙基溴化镁 作用下， 反应 11.08h， 生成
  参考文献：
  名称：

  Three-Component Intramolecular Two-Alkyne Annulations of Fischer Carbene Complexes: New Strategies for Steroid Synthesis

  摘要：

  The two-alkyne annulations of a variety of chromium and tungsten carbene complexes are examined in which both of the alkynes are tethered to the carbene complex. The reactions of complexes in which the two alkynes and the first alkyne and the carbene carbon are connected by methylene groups were investigated for their potential in the construction of tricyclic phenols. This methodology was screened for a number of different ring sizes, and it was found that the efficiency of phenol formation depended on the nature of the metal, the solvent, and the sizes of the rings produced. In the reactions of chromium complexes, for certain ring sizes an unprecedented lactone product was also observed which resulted from the incorporation of the two alkynes as well as two carbon monoxide ligands from the metal. A new strategy for entry to the tetracyclic ring system of steroids is developed that involves a tandem coupling of a Diels-Alder reaction of carbene complexes with the double-intramolecular two-alkyne annulation. In a model system where the A and C rings are aromatic, the feasibility of this strategy was demonstrated in a reaction where all four rings of the steroid ring system can be generated in a one-pot reaction. In a second generation of this strategy, it was demonstrated that the tandem coupling of these reactions can also lead to the generation of nonaromatic steroidal ring systems.

  DOI：

  10.1021/ja00096a019

文献信息

• Three-Component Intramolecular Two-Alkyne Annulations of Fischer Carbene Complexes: New Strategies for Steroid Synthesis
  作者：Jianming Bao、William D. Wulff、Vera Dragisich、Steve Wenglowsky、Richard G. Ball

  DOI：10.1021/ja00096a019

  日期：1994.8

  The two-alkyne annulations of a variety of chromium and tungsten carbene complexes are examined in which both of the alkynes are tethered to the carbene complex. The reactions of complexes in which the two alkynes and the first alkyne and the carbene carbon are connected by methylene groups were investigated for their potential in the construction of tricyclic phenols. This methodology was screened for a number of different ring sizes, and it was found that the efficiency of phenol formation depended on the nature of the metal, the solvent, and the sizes of the rings produced. In the reactions of chromium complexes, for certain ring sizes an unprecedented lactone product was also observed which resulted from the incorporation of the two alkynes as well as two carbon monoxide ligands from the metal. A new strategy for entry to the tetracyclic ring system of steroids is developed that involves a tandem coupling of a Diels-Alder reaction of carbene complexes with the double-intramolecular two-alkyne annulation. In a model system where the A and C rings are aromatic, the feasibility of this strategy was demonstrated in a reaction where all four rings of the steroid ring system can be generated in a one-pot reaction. In a second generation of this strategy, it was demonstrated that the tandem coupling of these reactions can also lead to the generation of nonaromatic steroidal ring systems.